CN112771118B - A Sintered Powder (SP) comprising a first polyamide component (PA 1) and a second polyamide component (PA 2), wherein the melting point of the second polyamide component (PA 2) is higher than the melting point of the first polyamide component (PA 1) - Google Patents
A Sintered Powder (SP) comprising a first polyamide component (PA 1) and a second polyamide component (PA 2), wherein the melting point of the second polyamide component (PA 2) is higher than the melting point of the first polyamide component (PA 1) Download PDFInfo
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- CN112771118B CN112771118B CN201980062666.0A CN201980062666A CN112771118B CN 112771118 B CN112771118 B CN 112771118B CN 201980062666 A CN201980062666 A CN 201980062666A CN 112771118 B CN112771118 B CN 112771118B
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- 239000000843 powder Substances 0.000 title claims abstract description 185
- 239000004952 Polyamide Substances 0.000 title claims abstract description 116
- 229920002647 polyamide Polymers 0.000 title claims abstract description 116
- 238000002844 melting Methods 0.000 title claims abstract description 77
- 230000008018 melting Effects 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 57
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 57
- 239000002245 particle Substances 0.000 claims description 31
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- 230000000977 initiatory effect Effects 0.000 claims description 18
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 17
- 239000012744 reinforcing agent Substances 0.000 claims description 17
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 13
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 11
- 101150118680 aflR gene Proteins 0.000 claims description 11
- 229920006528 PA66/6 Polymers 0.000 claims description 4
- 229920000577 Nylon 6/66 Polymers 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- 229920002292 Nylon 6 Polymers 0.000 description 30
- 239000000203 mixture Substances 0.000 description 23
- 229910000323 aluminium silicate Inorganic materials 0.000 description 19
- 239000000835 fiber Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 15
- 238000000110 selective laser sintering Methods 0.000 description 15
- 239000000976 ink Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 238000000113 differential scanning calorimetry Methods 0.000 description 12
- 230000005855 radiation Effects 0.000 description 12
- 238000000227 grinding Methods 0.000 description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000009699 high-speed sintering Methods 0.000 description 9
- 239000011324 bead Substances 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 238000009434 installation Methods 0.000 description 7
- 230000002787 reinforcement Effects 0.000 description 7
- 239000005995 Aluminium silicate Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 229910052622 kaolinite Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007431 microscopic evaluation Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000002821 anti-nucleating effect Effects 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002482 conductive additive Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000003623 enhancer Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000012815 thermoplastic material Substances 0.000 description 3
- 229920002748 Basalt fiber Polymers 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920006060 Grivory® Polymers 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920006020 amorphous polyamide Polymers 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920006374 copolyamide PA6I/6T Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000013213 extrapolation Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000000569 multi-angle light scattering Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QEFDIAQGSDRHQW-UHFFFAOYSA-N [O-2].[Cr+3].[Fe+2] Chemical class [O-2].[Cr+3].[Fe+2] QEFDIAQGSDRHQW-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 229910052849 andalusite Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
- C09D177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
- C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/031—Powdery paints characterised by particle size or shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/141—Processes of additive manufacturing using only solid materials
- B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a Sintered Powder (SP) comprising a first polyamide component (PA 1) and a second polyamide component (PA 2), wherein the melting point of the second polyamide component (PA 2) is higher than the melting point of the first polyamide component (PA 1). The invention also relates to a method for producing shaped bodies by sintering Sintered Powders (SP) or by the FFF (fuse manufacturing) method and to shaped bodies obtainable by the method according to the invention. The invention also relates to a method for producing a Sintered Powder (SP).
Description
The invention relates to a Sintered Powder (SP) comprising a first polyamide component (PA 1) and a second polyamide component (PA 2), wherein the melting point of the second polyamide component (PA 2) is higher than the melting point of the first polyamide component (PA 1). The invention also relates to a method for producing shaped bodies by sintering Sintered Powders (SP) or by the FFF (fuse manufacturing (fused filament fabrication)) method and to shaped bodies obtainable by the method according to the invention. The invention also relates to a method for producing a Sintered Powder (SP).
Rapid prototyping is a problem that is often handled recently. One method that is particularly suitable for this so-called "rapid prototyping" (rapid prototyping) is Selective Laser Sintering (SLS). This involves selectively exposing the plastic powder in the chamber with a laser beam. Melting the powder; the molten particles coalesce and resolidify. The application of the plastic powder and subsequent exposure to the laser is repeated to mold the three-dimensional shaped body.
The selective laser sintering process for preparing shaped bodies from pulverulent polymers is described in detail in U.S. Pat. No. 6,136,948 and WO 96/06881.
Selective laser sintering is often too time consuming to produce relatively large quantities of shaped bodies, and thus High Speed Sintering (HSS) or "multiple jet melting technology (multijet fusion technology)" from HP (MJF) can be used to produce relatively large quantities of shaped bodies. In high speed sintering, by spraying an infrared absorbing ink onto the cross section of the component to be sintered and then exposing to an infrared light source, a higher processing speed is achieved compared to selective laser sintering.
The FFF method, which is also referred to as FDM (fused deposition modeling) method, is a manufacturing method for preparing a molded body from a fusible plastic layer by layer. The shaped bodies are generally produced by extrusion of thermoplastic materials through a nozzle. For this purpose, the thermoplastic material is extruded in molten form through a nozzle and transferred into a construction space (construction space), in which it is hardened again. The nozzle is generally heated, so that the thermoplastic material is heated to a temperature above the melting point or glass transition temperature, and is subsequently deposited into the installation space by means of the nozzle, so that the three-dimensional shaped body is produced in a layer-by-layer manner.
In selective laser sintering, high-speed sintering or so-called multi-jet fusion techniques, the heating generally provides the structural space for the Sintered Powder (SP). The temperature of the installation space is generally higher than the melting temperature (T) M ) In the range of 5 to 50K low, thereby minimizing the energy input required to melt sinter the powder (SP) during exposure.
Due to the upper limit of the processing temperature of laser sintering and high-speed sintering equipment, in these 3D powder methods, only polyamides with high melting points can be processed with high complexity. Furthermore, high-melting polyamides additionally have a tendency for the shaped body to not melt effectively in the section of the shaped body to be sintered, which can lead to warpage of the component. Due to the high space temperature, the high-melting polyamides react even with very small amounts of residual oxygen, which gives shaped bodies with a pronounced brown discoloration.
Low-melting polyamides can generally be processed efficiently because molded articles can be produced at relatively low space temperatures. However, the shaped bodies thus obtained often exhibit inadequate resistance to thermal deformation and therefore cannot be used in applications requiring higher temperatures.
The prior art (Mechanical properties of PA6/PA12 blend specimens prepared by selective laser sintering, polymer Testing 31 (2012) 411-416, doi:10.1016) describes the mechanical properties of shaped bodies produced by selective laser sintering of polyamide powders. The polyamide powder used is a mixture of PA6 and PA 12. However, the ultimate strength of the test specimens prepared from the powder mixtures is much poorer than that of the test specimens prepared from the pure PA6 powder or the pure PA12 powder.
Sintered powders based on nylon-6 and nylon-12 as described in the prior art can be processed by means of selective laser sintering to obtain shaped bodies.
The object of the present invention is to provide an alternative Sintered Powder (SP). The sintered powder can be processed at relatively low space temperatures. Additionally, the resulting molded article has better heat distortion resistance than can be obtained by processing a low melting polyamide. Additionally, shaped bodies made from the sintered powder have better ultimate strength than those obtainable from the powder mixtures described in the prior art.
This object is achieved by a Sinter Powder (SP) comprising:
(A) At least one first polyamide component (PA 1) comprising at least 50 wt.% of a first aliphatic polyamide (aPA 1), based on the total weight of the first polyamide component (PA 1), wherein the first polyamide component (PA 1) has a first melting point (T M 1) And wherein the first aliphatic polyamide (aPA 1) consists of CH per repeating unit 2 A first ratio (V1) of groups to NHCO groups is in the range of 4 to 6,
(B) At least one second polyamide component (PA 2) comprising at least 50 wt.% of a second aliphatic polyamide (aPA) based on the total weight of the second polyamide component (PA 2), wherein the second polyamide component (PA 2) has a second melting point (T M 2) And wherein the second aliphatic polyamide (aPA 2) is composed of CH per repeating unit 2 A second ratio of groups to NHCO groups (V2) is in the range of 4 to 6,
(C) Optionally at least one free-flowing additive,
(D) Optionally at least one additive, and
(E) Optionally at least one reinforcing agent, wherein the second melting point (T M 2) Above the first melting point (T) M 1) And wherein the quotient (Q) of the value of the second ratio (V2) divided by the value of the first ratio (V1) is in the range of 0.6 to 1.5.
It has been found that, surprisingly, the Sinter Powder (SP) according to the invention can be processed at relatively low space temperatures to give shaped bodies having a relatively high resistance to thermal deformation.
Additionally, the Sintering Powder (SP) of the present invention can be effectively used for a selective laser sintering method, a high-speed sintering method, a multi-jet melting method, and a fuse manufacturing method.
The Sintered Powder (SP) of the present invention is explained in detail hereinafter.
Sintered Powder (SP)
According to the invention, the Sinter Powder (SP) comprises at least one first polyamide component (PA 1) as component (A), at least one second polyamide component (PA 2) as component (B), optionally at least one free-flowing auxiliary as component (C), optionally at least one additive as component (D) and optionally at least one reinforcing agent as component (E).
In the context of the present invention, the terms "component (a)" and "at least one first polyamide component (PA 1)" are used synonymously and thus have the same meaning. The same applies to the terms "component (B)" and "at least one second polyamide component (PA 2)". These terms are also synonymously used in the context of the present invention and thus have the same meaning.
Thus, the terms "component (C)" and "at least one free-flowing aid", "component (D)" and "at least one additive" and "component (E)" and "at least one enhancer" are also each synonymously used in the context of the invention and thus have the same meaning.
In a preferred embodiment, the Sinter Powder (SP) comprises from 5 to 95% by weight of component (a), from 5 to 95% by weight of component (B), from 0 to 5% by weight of component (C), from 0 to 5% by weight of component (D) and from 0 to 40% by weight of component (E), in each case based on the total weight of the Sinter Powder (SP).
The weight percentages of components (A), (B) and optionally components (C), (D) and (E) generally add up to 100% by weight.
The invention therefore also provides a Sintered Powder (SP) according to any one of claims 1 to 3, wherein the Sintered Powder (SP) comprises:
From 5 to 95% by weight of component (A),
from 5 to 95% by weight of component (B),
from 0 to 5% by weight of component (C),
0 to 5% by weight of component (D), and
from 0 to 40% by weight of component (E),
in each case based on the total weight of the Sinter Powder (SP).
In a particularly preferred embodiment, the Sinter Powder (SP) comprises from 10 to 90% by weight of component (a), from 10 to 90% by weight of component (B), from 0.1 to 2% by weight of component (C), from 0.1 to 2.5% by weight of component (D) and from 0 to 40% by weight of component (E), in each case based on the total weight of the Sinter Powder (SP).
Accordingly, the present invention also provides a Sintered Powder (SP), wherein the Sintered Powder (SP) comprises:
10 to 90% by weight of component (A),
10 to 90% by weight of component (B),
0.1 to 1% by weight of component (C),
0.1 to 2.5% by weight of component (D), and
from 0 to 40% by weight of component (E),
in each case based on the total weight of the Sinter Powder (SP).
In a particularly preferred embodiment, the Sinter Powder (SP) comprises 20 to 80 wt.% of component (a), 80 to 20 wt.% of component (B), 0.1 to 1 wt.% of component (C), 0.1 to 2 wt.% of component (D) and 0 to 40 wt.% of component (E), in each case based on the total weight of the Sinter Powder (SP).
In a most preferred embodiment, the Sinter Powder (SP) comprises from 25 to 75 wt.% of component (a), from 75 to 25 wt.% of component (B), from 0.1 to 0.5 wt.% of component (C), from 0.1 to 1.5 wt.% of component (D), and from 0 to 40 wt.% of component (E), in each case based on the total weight of the Sinter Powder (SP).
The Sintered Powder (SP) contains particles. The size (D50) of these particles is, for example, in the range from 10 to 250. Mu.m, preferably in the range from 15 to 200. Mu.m, more preferably in the range from 20 to 120. Mu.m, particularly preferably in the range from 20 to 110. Mu.m.
The Sintered Powder (SP) of the present invention comprises, for example:
d10 in the range of 10 to 60 μm,
d50 in the range of 25 to 90 μm, and
d90 in the range of 50 to 150 μm.
Preferably, the Sintered Powder (SP) of the present invention has:
d10 in the range of 20 to 50 μm,
d50 in the range of 40 to 90 μm, and
d90 in the range of 80 to 125 μm.
Accordingly, the present invention also provides a method wherein the Sintered Powder (SP) has:
d10 in the range of 10 to 60 μm,
d50 in the range of 25 to 90 μm, and
d90 in the range of 50 to 150 μm.
The invention therefore also provides a Sintered Powder (SP) in which the median particle size (D50) is in the range from 10 to 250. Mu.m.
In the context of the present invention, "D10" is understood to mean the following particle size: at this particle size, 10% by volume of the particles, based on the total volume of the particles, are less than or equal to D10, and 90% by volume of the particles, based on the total volume of the particles, are greater than D10. Similarly, "D50" is understood to mean the following particle size: at this particle size, 50% by volume of the particles, based on the total volume of the particles, are less than or equal to D50, and 50% by volume of the particles, based on the total volume of the particles, are greater than D50. Accordingly, "D90" is understood to mean the following particle size: at this particle size, 90% by volume of the particles, based on the total volume of the particles, are less than or equal to D90, and 10% by volume of the particles, based on the total volume of the particles, are greater than D90.
For determining the particle size, the Sintered Powder (SP) is suspended in a dry state using compressed air, or in a solvent (e.g., water or ethanol), and the suspension is analyzed. D10, D50 and D90 values were determined by laser diffraction using Malvern Mastersizer 3000. Evaluation was by Fraunhofer diffraction.
The Sintered Powder (SP) generally has a first melting point (T) in the range of 150 to 280 DEG C M 1). Preferably, the melting temperature (T) M 1) In the range of 160 to 270 c, Particularly preferably in the range of 170 to 265 ℃.
The Sintered Powder (SP) generally has a second melting point (T) in the range of 170 to 300 DEG C M 2). Preferably, the melting temperature (T) M 2) In the range from 180 to 310℃and particularly preferably in the range from 190 to 300 ℃.
In the context of the present invention, the melting point (T M 1) Sum (T) M 2) As determined by Differential Scanning Calorimetry (DSC). Typically, a heating operation (H) and a cooling operation (C) are measured, each at a heating rate/cooling rate of 20K/min. This provides a DSC profile as shown in figure 1, for example. Melting temperature (T) M ) It is understood to mean the temperature at which the melting peak of the heating operation (H) of the DSC profile has a maximum value.
The Sinter Powder (SP) generally also has a first crystallization temperature (T) in the range from 130 to 260 DEG C C 1). Preferably, the first crystallization temperature (T) of the Sintered Powder (SP) C 1) In the range from 140 to 250℃and particularly preferably in the range from 145 to 245 ℃.
The Sinter Powder (SP) generally also has a second crystallization temperature (T) in the range from 150 to 300 DEG C C 2). Preferably, the second crystallization temperature (T) of the Sintered Powder (SP) C 1) In the range from 160 to 290℃and particularly preferably in the range from 165 to 285 ℃.
In the context of the present invention, the crystallization temperature (T C 1) Sum (T) C 2) As determined by Differential Scanning Calorimetry (DSC). This generally involves measuring a heating operation (H) and a cooling operation (C), each at a heating rate/cooling rate of 20K/min. This provides a DSC profile as shown in figure 1, for example. Crystallization temperature (T) C ) The temperature at which the crystallization peak of the DSC curve is minimum.
The Sinter Powder (SP) also usually has a sintering window (W SP ) Reference is made to the second melting point (T) of the second polyamide component (PA 2) present in the Sinter Powder (SP) M 2). As described below, the firing window (W SP ) Is the onset temperature of melting (T M2 Initiation ) With the onset temperature of crystallization (T C2 Initiation ) The difference between them. Onset temperature of melting (T) M2 Initiation ) And onset temperature of crystallization (T C2 Initiation ) The measurement is performed as follows.
Sintering window (W) for Sintering Powder (SP) SP ) For example in the range from 10K to 40K (Kelvin), more preferably in the range from 15K to 35K, particularly preferably in the range from 18K to 33K.
The Sinter Powder (SP) may be prepared by any method known to those skilled in the art. The Sinter Powder (SP) is preferably prepared by grinding.
Suitable mills include all mills known to the person skilled in the art, for example classifier mills, opposed jet mills, hammer mills, ball mills, vibration mills or rotor mills such as pin disk mills and cyclone mills.
Grinding in the mill may likewise be carried out by any method known to the person skilled in the art. For example, milling may be performed under inert gas and/or while cooling with liquid nitrogen. Preferably with liquid nitrogen. The temperature during polishing is a desired temperature; the milling is preferably carried out at liquid nitrogen temperature, for example at a temperature in the range of-210 ℃ to-195 ℃. In this case, the temperature of the components at the time of grinding is, for example, in the range of-40℃to-30 ℃.
Grinding may be performed by any method known to those skilled in the art; for example, components (a), (B) and (C) and optionally (D), (E) and (F) are introduced into a mill and milled therein.
In one embodiment, the components are first mixed with each other and then ground. In this case, the method of preparing the Sintered Powder (SP) preferably includes the steps of:
a1 Mixing the following components:
(A) At least one first polyamide component (PA 1),
(B) At least one second polyamide component (PA 2),
(D) Optionally at least one additive, and
(E) Optionally at least one of the reinforcing agents,
b1 Grinding the mixture obtained in step a) to obtain a Sintered Powder (SP).
In a preferred embodiment, component (C) is mixed with the Sinter Powder (SP) after grinding.
In a preferred embodiment, the first polyamide component (PA 1) and the second polyamide component (PA 2) are provided separately from each other and subsequently mixed. The present invention therefore also provides a process for preparing a Sinter Powder (SP), comprising the steps of
a) Providing a first polyamide component (PA 1)
b) Providing a second polyamide component (PA 2)
c) The first polyamide component (PA 1) and the second polyamide component (PA 2) are mixed.
In a preferred embodiment, the first polyamide component (PA 1) and the second polyamide component (PA 2) are both provided in powder form and subsequently mixed in dry form (dry blending). The particle size of the first polyamide component (PA 1) and the second polyamide component (PA 2) is preferably within the particle size range of the Sinter Powder (SP), and thus the details and preferences given for the Sinter Powder (SP) are correspondingly applicable to the first polyamide component (PA 1) and the second polyamide component (PA 2).
The first polyamide component (PA 1) is preferably provided in process step a) by grinding, in this connection the details and preferred cases given above apply correspondingly thereto. The second polyamide component (PA 2) is likewise preferably provided in process step b) by grinding, and the details and preferences given above apply accordingly.
If in a preferred embodiment the Sinter Powder (SP) comprises components (D) and (E), these are mixed into the first polyamide component (PA 1) and/or the second polyamide component (PA 2), preferably in a twin-screw extruder. The amounts of any components (D) and (E) mixed in are selected such that the finished Sintered Powder (SP) contains the above amounts of components (D) and (E).
In a particularly preferred embodiment, the first polyamide component (PA 1) is provided in process step a) by: mixing and then grinding the first polyamide component (PA 1) with component (D) and optionally component (E) in a twin-screw extruder, this gives a first powder (P1), which is then mixed with component (C), and the second polyamide component (PA 2) is provided by: the second polyamide component (PA 2) is mixed with component (D) and optionally component (E) in a twin-screw extruder and subsequently ground to give a second powder (P2), which is subsequently mixed with component (C). The powders (P1) and (P2) obtained in method steps a) and b) are preferably subsequently mixed in dry form in method step c), which yields a Sintered Powder (SP).
The details and preferences mentioned above apply correspondingly for the grinding in method steps a) and b).
Component (A)
According to the invention, component (A) is at least one first polyamide component (PA 1). In the context of the present invention, the terms "component (a)" and "at least one first polyamide component (PA 1)" are used synonymously and thus have the same meaning. In the context of the present invention, "at least one first polyamide component (PA 1)" means exactly one first polyamide component (PA 1) or a mixture of two or more first polyamide components (PA 1). Preferably, component (a) is exactly one first polyamide component (PA 1).
The at least one first polyamide component (PA 1) comprises at least 50 wt.% of a first aliphatic polyamide (aPA 1) based on the total weight of the first polyamide component (PA 1). The first aliphatic polyamide (aPA 1) is composed of CH per repeating unit 2 The first ratio (V1) of groups to NHCO groups is in the range of 4 to 6.
Those skilled in the art know that aliphatic polyamides are made from polymers having CH 2 Repeating units of groups and NHCO groups are formed. For example, nylon-6, 6 has the following repeating units (base units):
thus, nylon-6, 6 contains 10 CH's in the base unit 2 Groups and 2 NHCO groups, resulting in CH of PA 66 2 The ratio of groups to NHCO groups was 5.
The following table shows, for example, the CH of some polyamides 2 Ratio of groups to NHCO groups.
| Polyamide | CH 2 /NHCO |
| 4 | 3 |
| 46 | 4 |
| 5 | 4 |
| 6 | 5 |
| 66 | 5 |
| 7 | 6 |
| 8 | 7 |
| 9 | 8 |
| 69 | 6.5 |
| 610 | 7 |
| 612 | 8 |
| 10 | 9 |
| 11 | 10 |
| 12 | 11 |
The first polyamide component (PA 1) has a second melting point (T) which is lower than that of the second polyamide component (PA 2) M 2) Is of the first melting point (T) M 1). First melting Point (T) M 1) Preferably higher than the second melting point (T M 2) 20 to 70K lower.
Preferably, the first melting point (T M 1) In the range from 150 to 280 ℃, more preferably in the range from 170 to 270 ℃, particularly preferably in the range from 175 to 265 ℃, measured according to ISO 11357-3:2014.
Suitable first polyamide components (PA 1) have a weight average molecular weight (M) in the range from 500 to 2 000g/mol, preferably in the range from 10 000 to 90 g/mol, particularly preferably in the range from 20 to 70 g/mol w(PA1) ). Weight average molecular weight (M) w(PA1) ) According to Chi-san Wu, "Handbook of size exclusion chromatography and related techniques" page 19 was determined by SEC-MALLS (size exclusion chromatography-Multi-angle laser light Scattering).
Examples of suitable first aliphatic polyamides (aPA 1) are aliphatic polyamides derived from lactams having 5 to 7 ring members. Examples of the first aliphatic polyamide (aPA 1) derived from a lactam include polyamides derived from polycaprolactam and/or polyazacyclo-octanone (poly 1-aza-2-cyclooctanone), with polycaprolactam being preferred.
The preferred first aliphatic polyamide (aPA 1) is at least one aliphatic polyamide selected from the group consisting of PA 5, PA 6/66, PA 6 and PA 66/6.
The PA 6/66 preferably has a caprolactam unit content of from 60 to 95% by weight, based on the total weight proportion of PA 6/66. Nylon-66/6 preferably has from 5 to 40 wt% caprolactam units, based on the total weight of PA 66/6.
The first aliphatic polyamide (aPA 1) is preferably at least one aliphatic polyamide selected from the group consisting of PA 6, PA 6/66 and PA 66/6.
Nylon-6/66 preferably has a melting point in the range of 185 to 205 ℃. Nylon-6 preferably has a melting point in the range of 211 to 229 ℃. Nylon-66/6 preferably has a melting point of 221 to 239 ℃.
CH in the first aliphatic polyamide (aPA 1) 2 The first ratio (V1) of groups to NHCO groups is preferably in the range of 4.5 to 5.5, particularly preferably in the range of 4.8 to 5.2, more preferably in the range of 4.9 to 5.1, particularly preferably in the range of 4.95 to 5.05.
The first polyamide component (PA 1) preferably comprises 50 to 90 wt.% of the first aliphatic polyamide (aPA 1), more preferably 60 to 80 wt.% of the first aliphatic polyamide (aPA 1), in each case based on the total weight of the first polyamide component (PA 1).
Preferably, the first polyamide component (PA 1) comprises 50 to 90 wt.%, more preferably 60 to 80 wt.% of the first aliphatic polyamide (aPA 1) and 10 to 50 wt.%, more preferably 20 to 40 wt.% of the first (semi) aromatic polyamide (arPA 1), in each case based on the total weight of the first polyamide component (PA 1).
Preferably, the first (semi) aromatic polyamide (arPA 1) is an amorphous polyamide. Further preferably, the (semi) aromatic polyamide (arPA 1) is at least one (semi) aromatic polyamide selected from the group consisting of PA 6I/6T, PA I and PA 6/3T, with PA 6I/6T being particularly preferred.
Component (B)
According to the invention, component (B) is at least one second polyamide component (PA 2). In the context of the present invention, the terms "component (B)" and "at least one second polyamide component (PA 2)" are used synonymously and thus have the same meaning. In the context of the present invention, "at least one second polyamide component (PA 2)" means exactly one second polyamide component (PA 2) or a mixture of two or more second polyamide components (PA 2). Preferably, component (B) is exactly one second polyamide component (PA 2).
The second polyamide component (PA 2) is different from component (PA 1). The second aliphatic polyamide (aPA 1) is different from the first aliphatic polyamide (aPA).
The second polyamide component (PA 2) has a first melting point (T) which is higher than that of the first polyamide component (PA 1) M 1) Is of the second melting point (T) M 2). Second melting Point (T) M 2) Preferably higher than the first melting point (T) M 1) 20 to 70K high.
Second melting Point (T) M 2) Preferably in the range of 170 to 300℃as determined according to ISO 11357-3:2014.
Suitable second polyamide components (PA 2) have a weight average molecular weight (M) in the range from 500 to 2 000g/mol, preferably in the range from 10 000 to 90 g/mol, particularly preferably in the range from 20 to 70 g/mol w(PA2) ). Weight average molecular weight (M) w(PA2) ) According to Chi-san Wu, "Handbook of size exclusion chromatography and related techniques" page 19 was determined by SEC-MALLS (size exclusion chromatography-Multi-angle laser light Scattering).
The preferred second aliphatic polyamide (aPA 2) is at least one aliphatic polyamide selected from the group consisting of PA46, PA 5, PA 6, PA 66/6 and PA 66. The polyamide PA46 preferably has a melting point in the range of 285 to 290 ℃.
The second aliphatic polyamide (aPA 2) is preferably at least one aliphatic polyamide selected from the group consisting of PA 6, PA 66/6 and PA 66.
Nylon-6, 6 preferably has a melting point in the range of 250 to 270 ℃.
The second ratio (V2) is preferably in the range from 4.5 to 5.5, particularly preferably in the range from 4.8 to 5.2, more preferably in the range from 4.9 to 5.1, particularly preferably in the range from 4.95 to 5.05. According to the invention, the quotient (Q) of the value of the second ratio (V2) divided by the value of the first ratio (V1) is in the range from 0.6 to 1.5, preferably in the range from 0.8 to 1.2, particularly preferably in the range from 0.9 to 1.1, more preferably in the range from 0.96 to 1.04, particularly preferably in the range from 0.98 to 1.02.
The quotient is defined by the following mathematical expression.
At least one second polyamide component (PA 2) comprising at least 50 wt.%, based on the total weight of the second polyamide component (PA 2), of a polymer having a second melting point (T M 2) Is a second aliphatic polyamide (aPA 2). The second aliphatic polyamide (aPA 2) is composed of CH per repeating unit 2 A second ratio of groups to NHCO groups (V2) is in the range of 4 to 6.
The second polyamide component (PA 2) comprises preferably 50 to 100 wt.% of the second aliphatic polyamide (aPA 2), more preferably 60 to 100 wt.% of the second aliphatic polyamide (aPA 2), based in each case on the total weight of the second polyamide component (PA 2).
Preferably, the second polyamide component (PA 2) comprises 50 to 90 wt.%, more preferably 60 to 80 wt.% of the second aliphatic polyamide (aPA 2) and 10 to 50 wt.%, more preferably 20 to 40 wt.% of the second (semi) aromatic polyamide (arPA 2), in each case based on the total weight of the second polyamide component (PA 2).
Preferably, the second (semi) aromatic polyamide (arPA 2) is an amorphous polyamide. Further preferably, the second (semi) aromatic polyamide (arPA 2) is at least one (semi) aromatic polyamide selected from the group consisting of PA 6I/6T, PA I and PA 6/3T, with PA 6I/6T being particularly preferred. Preferably, the second polyamide component (PA 2) is the same (semi) aromatic polyamide as the first polyamide component (PA 1). In this embodiment, the second (semi) aromatic polyamide (arPA 2) is the same as the first (semi) aromatic polyamide (arPA 1).
The invention therefore also provides a Sinter Powder (SP), wherein the first polyamide component (PA 1) comprises 50 to 90 wt.%, based on the total weight of the first polyamide component (PA 1), of a first aliphatic polyamide (aPA) selected from PA6/66, PA6 and PA66/6 and 10 to 50 wt.%, of a first (semi) aromatic polyamide (arPA 1), and the second polyamide component (PA 2) comprises 50 to 90 wt.%, based on the total weight of the second polyamide component (PA 2), of a second aliphatic polyamide (aPA 2) selected from PA6, PA66/6 and PA66 and 10 to 50 wt.%, of a second (semi) aromatic polyamide (arPA 2).
In another preferred embodiment, the second polyamide component (PA 2) does not contain any (semi) aromatic polyamide (arPA 2).
Component (C)
According to the invention, component (C) is at least one free-flowing auxiliary. In the context of the present invention, the terms "component (C)" and "at least one free-flowing aid" are used synonymously and thus have the same meaning. In the context of the present invention, "at least one free-flowing aid" means exactly one free-flowing aid or a mixture of two or more free-flowing aids. If the Sinter Powder (SP) comprises component (C), component (C) is preferably exactly one free-flowing aid or a mixture of two free-flowing aids.
Suitable free-flowing auxiliaries are, for example, silicon dioxide or aluminum oxide. One example of a suitable alumina is from EvonikAlu C。
Component (D)
Component (D) is at least one additive.
In the context of the present invention, "at least one additive" means exactly one additive or a mixture of two or more additives.
Additives are known per se to the person skilled in the art. For example, the at least one additive is selected from the group consisting of anti-nucleating agents, stabilizers, conductive additives, end-group functionalizing agents, dyes, antioxidants (preferably sterically hindered phenols) and colored pigments.
The present invention therefore also provides a process wherein component (D) is selected from the group consisting of anti-nucleating agents, stabilizers, conductive additives, end-group functionalizing agents, dyes, antioxidants (preferably sterically hindered phenols) and colored pigments.
An example of a suitable anti-nucleating agent is lithium chloride. Suitable stabilizers are, for example, phenol, phosphite and copper stabilizers. Suitable conductive additives are carbon fibers, metals, stainless steel fibers, carbon nanotubes and carbon black. Suitable end-group functionalizing agents are, for example, terephthalic acid, adipic acid, and propionic acid. Suitable dyes and colored pigments are, for example, carbon black and iron chromium oxides.
Examples of suitable antioxidants are those from BASF SE245 or->1098。
If the sinter powder comprises component (D), it comprises at least 0.1% by weight, preferably at least 0.2% by weight, based on the sum of the weight proportions of components (A), (B), (C), (D) and (E), component (D), preferably based on the total weight of the Sinter Powder (SP).
Component (E)
According to the invention, any component (E) present is at least one reinforcing agent.
In the context of the present invention, "at least one reinforcing agent" means exactly one reinforcing agent or a mixture of two or more reinforcing agents.
In the context of the present invention, reinforcing agent is understood to be a material which improves the mechanical properties of the shaped bodies produced by the process according to the invention compared to shaped bodies which do not contain reinforcing agent.
Reinforcing agents are known per se to the person skilled in the art. Component (E) may be in the form of spheres, flakes or fibers, for example.
Preferably, the at least one reinforcing agent is in the form of platelets or fibers.
"fiber reinforcement" is understood to mean a reinforcement in which the ratio of the length of the fiber reinforcement to the diameter of the fiber reinforcement is in the range from 2:1 to 40:1, preferably in the range from 3:1 to 30:1, particularly preferably in the range from 5:1 to 20:1, wherein the length of the fiber reinforcement and the diameter of the fiber reinforcement are determined by microscopic evaluation of the sample after ashing, wherein at least 70 parts of fiber reinforcement after ashing are evaluated.
In this case, the length of the fiber-reinforced agent is usually in the range of 5 μm to 1,000. Mu.m, preferably in the range of 10 μm to 600. Mu.m, particularly preferably in the range of 20 μm to 500. Mu.m, as determined by microscopic evaluation in an image after ashing.
In this case, the diameter is, for example, in the range of 1 μm to 30 μm, preferably in the range of 2 μm to 20 μm, particularly preferably in the range of 5 μm to 15 μm, as determined by microscopic evaluation of the ashed image.
In another preferred embodiment, the at least one enhancer is in the form of a tablet. In the context of the present invention, "platelet form" is understood to mean that the particles of the at least one reinforcing agent have a diameter to thickness ratio in the range from 4:1 to 10:1, as determined by microscopic evaluation of the ashed image.
Suitable reinforcing agents are known to the person skilled in the art and are selected from, for example, carbon nanotubes, carbon fibers, boron fibers, glass beads, silica fibers, ceramic fibers, basalt fibers, aluminosilicates, aramid fibers and polyester fibers.
Accordingly, the present invention also provides a process wherein component (E) is selected from the group consisting of carbon nanotubes, carbon fibers, boron fibers, glass beads, silica fibers, ceramic fibers, basalt fibers, aluminosilicates, aramid fibers, and polyester fibers.
The at least one reinforcing agent is preferably chosen from aluminosilicates, glass fibres, glass beads, silica fibres and carbon fibres.
More preferably, the at least one reinforcing agent is selected from the group consisting of aluminosilicates, glass fibres, glass beads and carbon fibres. These enhancers may additionally be amino-functionalized.
Suitable silica fibers are, for example, wollastonite.
Suitable aluminosilicates are known per se to the person skilled in the art. Aluminosilicate means containing Al 2 O 3 And SiO 2 Is a compound of (a). Structurally, the common factor in aluminosilicates is the silicon atom to be bound byOxygen atom tetrahedrally coordinates, and aluminum atoms are octahedral coordinates by oxygen atoms. The aluminosilicate may additionally comprise other elements.
Preferred aluminosilicates are sheet silicates. Particularly preferred aluminosilicates are calcined aluminosilicates, particularly preferably calcined sheet silicates. The aluminosilicates may additionally be amino-functionalized.
If at least one of the reinforcing agents is an aluminosilicate, the aluminosilicate may be used in any form. For example, it can be used in the form of pure aluminosilicates, but aluminosilicates can likewise be used in mineral form. Preferably, the aluminosilicate is used in mineral form. Suitable aluminosilicates are, for example, feldspar, zeolite, sodalite, sillimanite, andalusite and kaolin. Kaolin is a preferred aluminosilicate.
Kaolin is one of the claystone and essentially comprises the mineral kaolinite. The empirical mode of kaolinite is Al 2 [(OH) 4 /Si 2 O 5 ]. Kaolinite is a sheet silicate. In addition to kaolinite, kaolin generally comprises other compounds such as titanium dioxide, sodium oxide and iron oxide. The preferred kaolin according to the present invention comprises at least 98% by weight of kaolinite based on the total weight of the kaolin.
If the sinter powder comprises component (E), it preferably comprises at least 10% by weight of component (E) based on the sum of the weight percentages of components (A), (B), (C), (D) and (E), preferably based on the total weight of the Sinter Powder (SP).
The invention also provides a method for producing a shaped body, comprising the following steps: is) providing a layer of Sintered Powder (SP),
is) exposing the layer of Sintered Powder (SP) provided in step is) to form a shaped body.
Step is
In step is), a layer of Sintered Powder (SP) is provided.
The layer of Sintered Powder (SP) may be provided by any method known to a person skilled in the art. Layers of Sinter Powder (SP) are usually provided in the installation space on the installation platform. The temperature of the construction space can optionally be controlled.
The installation space has, for example, a first melting point (T) which is greater than the Sintered Powder (SP) M 1) A temperature of 1 to 100K (Kelvin) lower, preferably than the first melting point (T) of the Sintered Powder (SP) M 1) A temperature of 5 to 50K lower, particularly preferably lower than the first melting point (T) of the Sintered Powder (SP) M 1) A temperature of 10 to 25K lower.
The installation space has a temperature, for example, in the range from 150 to 250 ℃, preferably in the range from 160 to 230 ℃, particularly preferably in the range from 165 to 210 ℃.
The layer of Sintered Powder (SP) may be provided by any method known to a person skilled in the art. For example, the layer of Sinter Powder (SP) is provided by a coating rod or roller at the thickness to be achieved in the installation space.
The thickness of the layer of Sintered Powder (SP) provided in step is) may be as desired. For example, it is in the range of 50 to 300. Mu.m, preferably in the range of 70 to 200. Mu.m, particularly preferably in the range of 90 to 150. Mu.m.
Step is
In step is), the layer of Sintered Powder (SP) provided in step is) is exposed.
Upon exposure, at least a portion of the layer of Sintered Powder (SP) melts. The melted Sintered Powder (SP) coalesces and forms a homogeneous melt. After exposure, the melted portion of the layer of Sintered Powder (SP) is cooled again and the homogeneous melt is solidified again.
Suitable exposure methods include all methods known to those skilled in the art. Preferably, the exposing in step is) is performed with a radiation source. The radiation source is preferably selected from the group consisting of infrared light sources and lasers. Particularly preferred infrared light sources are near infrared light sources.
The invention thus also provides a method wherein the exposing in step is) is performed with a radiation source selected from the group consisting of a laser and an infrared light source.
Suitable lasers are known to the person skilled in the art and are, for example, fiber lasers, nd: YAG lasers (neodymium-doped yttrium aluminum garnet lasers) or carbon dioxide lasers. Carbon dioxide lasers typically have a wavelength of 10.6 μm.
If the radiation source used in the exposure in step is) is a laser, the layer of Sintered Powder (SP) provided in step is) is typically exposed locally and briefly to the laser beam. This selectively melts only the portion of the Sintered Powder (SP) that has been exposed to the laser beam. If a laser is used in step is), the method of the invention is also referred to as selective laser sintering. Selective laser sintering is known per se to those skilled in the art.
If the radiation source used in the exposure in step is) is an infrared light source, in particular a near infrared light source, the wavelength of the radiation source is generally in the range 780nm to 1000 μm, preferably in the range 780nm to 50 μm, in particular in the range 780nm to 2.5 μm.
In the exposure in step is), in this case, the entire Sintered Powder (SP) layer is generally exposed. In order to melt only a desired region of the Sintered Powder (SP) in the exposure, an infrared absorbing ink (IR absorbing ink) is generally applied to the region to be melted.
The process for producing the shaped bodies in this case preferably comprises, between step is) and step is), a step is-1) of applying at least one IR absorbing ink to at least a part of the layer of the Sinter Powder (SP) provided in step is).
Accordingly, the present invention further provides a process for preparing a shaped body, comprising the following steps: is) providing a layer of Sintered Powder (SP),
is-1) applying at least one IR absorbing ink to at least a portion of the layer of Sintered Powder (SP) provided in step is),
is) exposing the layer of Sintered Powder (SP) provided in step is) to which the IR absorbing ink is applied.
Suitable IR absorbing inks are all IR absorbing inks known to the person skilled in the art, in particular IR absorbing inks known to the person skilled in the art for high-speed sintering.
IR absorbing inks generally comprise at least one absorber which absorbs IR radiation, preferably NIR radiation (near infrared radiation). Upon exposure of the layer of Sinter Powder (SP) in step is), the IR radiation, preferably NIR radiation, is absorbed by the IR absorber present in the IR absorbing ink such that the portion of the layer of Sinter Powder (SP) to which the IR absorbing ink is applied is selectively heated.
The IR absorbing ink and the at least one absorber may comprise a carrier liquid. Suitable carrier liquids are known to the person skilled in the art and are, for example, oils or solvents.
At least one absorbent may be dissolved or dispersed in the carrier liquid.
If the exposure in step is) is performed with a radiation source selected from infrared light sources and if step is-1) is performed, the method of the invention is also referred to as a High Speed Sintering (HSS) or multi-jet Melting (MJF) method. Such methods are known per se to those skilled in the art.
After step is), the layer of the Sintering Powder (SP) is typically reduced by the layer thickness of the layer of the Sintering Powder (SP) provided in step i), and a further layer of Sintering Powder (SP) is applied. This is then exposed again in step is).
Bonding an upper layer of the Sintered Powder (SP) to a lower layer of the Sintered Powder (SP); furthermore, the particles of the Sintered Powder (SP) in the upper layer are bonded to each other by fusion.
Thus, in the process of the invention, steps is) and optionally is-1) may be repeated).
By repeatedly lowering the powder bed, applying the Sintered Powder (SP) and exposing, and thus melting the Sintered Powder (SP), a three-dimensional molded body is produced. For example, a molded article having a cavity can be produced. Since the unmelted Sintered Powder (SP) itself is used as a supporting material, an additional supporting material is not required.
The invention further provides a process for preparing a shaped body, comprising the following steps:
if) melt-Sintered Powder (SP)
iif) depositing a melt-Sintered Powder (SP) in the structural space to form a shaped body.
This method is also called FFF (fuse manufacturing) method. In this method, the shaped body is produced from a meltable plastic layer by layer. The shaped bodies are usually obtained by extruding the Sinter Powder (SP) in the molten state through a nozzleAnd (3) preparation. For this purpose, the Sinter Powder (SP) is melted in the method step if) and preferably extruded through a nozzle and transferred into a construction space, where it is hardened again. In another preferred embodiment, in step if), the Sinter Powder (SP) is first melted and extruded in an extruder to form strands. The strand is then preferably remelted in a nozzle. The nozzle is typically heated to heat the Sintered Powder (SP) above the second melting point (T M 2) Is then deposited in the construction space, preferably by means of a nozzle, in order to produce a three-dimensional shaped body in a layer-by-layer manner. Steps if) and iif) are typically repeated until the molded body is completed.
The invention further provides the use of the Sinter Powder (SP) in a sintering process or in a fuse manufacturing process.
The invention therefore further provides a shaped body obtainable by the process according to the invention.
Of particular importance in the process of the invention is the melting range of the Sinter Powder (SP), the sintering window (W) SP ) Reference is made to the second melting point (T M 2)。
Sintering window (W) for Sintering Powder (SP) SP ) Can be determined, for example, by Differential Scanning Calorimetry (DSC).
In differential scanning calorimetry, the temperature of the sample (i.e., the sample of the Sintered Powder (SP) in the case of the present invention) and the temperature of the reference are linearly varied with time. To this end, heat is applied/removed to/from the sample and the reference. The heat Q required to maintain the sample at the same temperature as the reference is measured. The heat QR applied to/removed from the reference is used as a reference value.
If the sample undergoes an endothermic phase change, additional heat Q must be applied to keep the sample at the same temperature as the reference. If an exothermic phase change occurs, a certain amount of heat Q must be removed to keep the sample at the same temperature as the reference. This measurement provides a DSC profile in which the amount of heat Q applied to/removed from the sample is plotted as a function of temperature T.
The measurement generally involves an initial heating operation (H), i.e. the sample and the reference are heated in a linear manner. During the melting of the sample (solid/liquid phase change), additional heat Q must be applied to keep the sample at the same temperature as the reference. In the DSC diagram, a peak called melting peak is then observed.
After the heating operation (H), the cooling operation (C) is typically measured. This involves linearly cooling the sample and reference, i.e. removing heat from the sample and reference. During crystallization/solidification (liquid/solid phase change) of the sample, a greater amount of heat Q must be removed to keep the sample at the same temperature as the reference due to the heat released during crystallization/solidification. In the DSC chart of the cooling operation (C), a peak called a crystallization peak is then observed in the opposite direction to the melting peak.
In the context of the present invention, heating during a heating operation is typically performed at a heating rate of 20K/min. In the context of the present invention, cooling during a cooling operation is typically performed at a cooling rate of 20K/min.
A DSC diagram including a heating operation (H) and a cooling operation (C) is depicted in fig. 1 by way of illustration. DSC plots can be used to determine the onset temperature (T) M2 Initiation ) And onset temperature of crystallization (T C2 Initiation )。
To determine the onset temperature of melting (T M2 Initiation ) Tangential lines are drawn relative to the baseline of heating operation (H) at temperatures below the melting peak. The second tangent line is drawn relative to the first inflection point of the melting peak at a temperature below the temperature at which the melting peak is at its maximum. The two tangent lines are extrapolated until they intersect. The intersection point of the vertical extrapolation to the temperature axis represents the onset temperature (T M2 Initiation )。
To determine the onset temperature of crystallization (T C2 Initiation ) Tangential line is drawn relative to the baseline of cooling operation (C) at a temperature above the crystallization peak. The second tangent line is drawn with respect to the inflection point of the crystallization peak at a temperature higher than the temperature at which the crystallization peak is at its minimum. The two tangent lines are extrapolated until they intersect. The intersection point of the vertical extrapolation to the temperature axis indicates the onset temperature (T C2 Initiation )。
The sintering window (W) is set from the melting start temperature (T M2 Initiation ) With the onset temperature of crystallization (T C2 Initiation ) The difference between them is obtained. Thus:
W＝T M2 initiation -T C2 Initiation 。
In the context of the present invention, the term "sintering window (W SP ) ", sintering window (W) SP ) And "the melting onset temperature (T) M2 Initiation ) With the onset temperature of crystallization (T C2 Initiation ) The differences between them "have the same meaning and are used synonymously.
The Sinter Powder (SP) of the invention is particularly suitable for sintering processes.
Molded body
The method of the present invention provides a molded article. After solidification of the Sintered Powder (SP) melted on exposure in step is) or iif), the shaped body can be removed directly from the powder bed. It is likewise possible to first cool the shaped body and then remove it only from the powder bed. Any adhering particles of unmelted Sintered Powder (SP) may be mechanically removed from the surface by known methods. Methods for surface treatment of the shaped bodies include, for example, vibratory grinding or barrel polishing, sand blasting, glass bead blasting or bead blasting.
The shaped bodies obtained can also be subjected to further processing or, for example, to surface treatment.
If step is-1) is carried out, the shaped bodies generally additionally comprise IR-absorbing ink.
It is clear to the person skilled in the art that due to the exposure of the Sintered Powder (SP), components (a), (B) and any (C) and any (D) and (E) can undergo chemical reactions and thus be changed. Such reactions are known to those skilled in the art.
Preferably, components (a), (B) and (C) and any (D), (E) and (F) do not undergo any chemical reaction upon exposure in step ii); whereas the Sintered Powder (SP) only melts.
Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
Examples
The following powders were used:
powder (P1)
The first polyamide component (PA 1) comprises 78.6% by weight of PA6 (nylon-6,B27E, BASF SE), 21 wt.% PA6I/6T (nylon-6I/6T,Grivory G16,EMS) and 0.4 wt.% Irganox->(component (D), N, N' -hexane-1, 6-diylbis (3- (3, 5-di-tert-butyl-4-hydroxyphenylpropionamide)), BASF SE), in weight percentages being based in each case on the total weight of component (A)
Powder (P2)
The second polyamide component (PA 2) comprises 78.5 wt.% PA66 (nylon-6, A27, BASF SE), 21 wt.% PA6I/6T (nylon-6I/6T,Grivory G16,EMS) and 0.5 wt.% Irganox->(component (D), N, N' -hexane-1, 6-diylbis (3- (3, 5-di-tert-butyl-4-hydroxyphenylpropionamide), BASF SE), in weight percentages being based in each case on the total weight of component (B)
Powder (P3)
The powder (P3) is a mixture of 75% by weight of powder (P1) and 25% by weight of glass beads (Sphermslass 3000CPO3, potters).
Table 1 reports the particle sizes and melting points and crystallization temperatures of powders (P1), (P2), (P3) and 70:30 mixtures and 50:50 mixtures of (P1) and (P2).
The powders (P1), (P2), (P3) and the mixture of the powders (P1) and (P2) were used for preparing molded bodies (sintered specimens of 80 mm. Times.10 mm. Times.4 mm) by selective laser sintering. The temperature of the structural space is 200 ℃; the energy input of the laser is 40mJ/mm 2 。
The measurement results of the sintered samples are shown in table 2.
Particle size, melting point and crystallization temperature were determined as described above in the specification.
Softening temperature "Vicat B50" is determined as follows: silicone oil was measured at a heating rate of 50K/h according to ISO 306:2013 at a sample thickness of 4mm and as a heat transfer medium.
The heat distortion temperature "HDT" is determined as follows: dried samples (80 ℃, reduced pressure, 336 hours) were measured at a heating rate of 120K/h according to ISO 72-2:2013 at a span of 64 mm.
TABLE 1
TABLE 2
DSC measurements of the sintered samples showed that the eutectic produced a partially compatible mixture. This is due to the first crystallization temperature T C 1 and a second crystallization temperature T C The decrease in 2 becomes apparent. The Vicat softening temperature of EB2 is higher than VP 1; which is additionally higher than in the case of VP 3. In addition, in the case of the Sintered Powder (SP) of the present invention, no segregation of the powder was observed, as in the case of VP 3. White sintered specimens were obtained from the Sintered Powders (SP) of the present invention.
The prior art (mechanical properties of PA6/PA12 mixed samples prepared by selective laser sintering), polymer test 31 (2012) 411-416, doi: 10.1016) describes the mechanical properties of shaped bodies prepared from polyamide powders by selective laser sintering. The mechanical properties of pure PA6 powder and of pure PA12 powder and PA6/PA12 powder mixtures are compared here. Disclosed herein is a reduction in impact resistance of 78% based on the ultimate strength of shaped bodies made from pure PA12 powder in the case of a 50:50 polyamide powder mixture of PA6:pa 12. For the polyamide powder mixture PA6/PA12 of 20:80, a reduction in ultimate strength of 47% is likewise observed, based on the ultimate strength of the shaped bodies prepared from the pure PA12 powder.
Table 3 below shows the test results of the ultimate strength of the sintered specimens prepared from the pure PA6 powder (see comparative example VP 1) or from the Sintered Powder (SP) of the present invention. EB1 shows the ultimate strength of sintered specimens prepared from 85:15 (wt%) P1:P2 powder mixtures. Inventive example EB4 shows the ultimate strength of sintered samples prepared from an 80:20 (wt%) P1:p2 powder mixture. Inventive example EB2 shows the strength of sintered samples prepared from 70:30 (wt%) of Sintered Powder (SP) P1:p 2.
For the inventive examples, the ultimate strength was measured in the dry state according to ISO 527-2:2012. For sintered specimens prepared from pure PA6 powder, the ultimate strength was measured to be 57.7MPa. For sintered samples prepared by laser sintering the powder mixtures EB1, EB2 and EB4 of the invention, the ultimate strengths were measured to be 51.8, 42 and 47.9MPa, respectively. Therefore, the ultimate strength is only reduced by 10.2%, 27.2% and 17.0%, respectively, based on the sintered specimens prepared from the pure PA6 powder, and is thus far lower than in the case of sintered specimens prepared from the powder mixtures according to the prior art. In the case of the present invention, the ultimate strength of the sintered specimens prepared from pure PA66 powder (see VP 2) cannot be determined, since sintering of the powder (VP 2) only gives sintered specimens which are very poor, highly discolored and thus cannot be tested.
TABLE 3 Table 3
Claims (13)
1. A Sintered Powder (SP) comprising the following components:
(A) At least one first polyamide component (PA 1) comprising at least 50 wt.% of a first aliphatic polyamide (aPA 1), based on the total weight of the first polyamide component (PA 1), wherein the first polyamideComponent (PA 1) has a first melting point (T) M 1) And wherein the first aliphatic polyamide (aPA 1) consists of CH per repeating unit 2 A first ratio (V1) of groups to NHCO groups is in the range of 4 to 6,
(B) At least one second polyamide component (PA 2) comprising at least 50 wt.% of a second aliphatic polyamide (aPA) based on the total weight of the second polyamide component (PA 2), wherein the second polyamide component (PA 2) has a second melting point (T M 2) And wherein the second aliphatic polyamide (aPA 2) is composed of CH per repeating unit 2 A second ratio of groups to NHCO groups (V2) is in the range of 4 to 6,
(C) Optionally at least one free-flowing additive,
(D) Optionally at least one additive, and
(E) Optionally at least one of the reinforcing agents,
wherein the second melting point (T) M 2) Above the first melting point (T) M 1) And wherein the quotient (Q) of the value of the second ratio (V2) divided by the value of the first ratio (V1) is in the range from 0.6 to 1.5,
wherein the first polyamide component (PA 1) comprises 50 to 90 wt.% of a first aliphatic polyamide (aPA) selected from PA6/66, PA6 and PA66/6 and 10 to 50 wt.% of a first aromatic or semi-aromatic polyamide (arPA 1) based on the total weight of the first polyamide component (PA 1), and the second polyamide component (PA 2) comprises 50 to 90 wt.% of a second aliphatic polyamide (aPA 2) selected from PA6, PA66/6 and PA66 and 10 to 50 wt.% of a second aromatic or semi-aromatic polyamide (arPA 2) based on the total weight of the second polyamide component (PA 2).
2. Sintered Powder (SP) according to claim 1, wherein the second melting point (T M 2) And a first melting point (T) M 1) The difference between them is in the range of 20 to 70K.
3. Sintered Powder (SP) according to claim 1 or 2, wherein the second melting point (T M 2) In the range of 170 to 300 ℃ and a first melting point (T M 1) In the range of 150 to 280 c.
4. The Sinter Powder (SP) according to claim 1, wherein the Sinter Powder (SP) comprises:
from 5 to 95% by weight of component (A),
from 5 to 95% by weight of component (B),
from 0 to 5% by weight of component (C),
0 to 5% by weight of component (D), and
from 0 to 40% by weight of component (E),
in each case based on the total weight of the Sinter Powder (SP).
5. Sintered Powder (SP) according to claim 1, wherein
A first ratio (V1) in the range of 4.5 to 5.5, and
a second ratio (V2) in the range of 4.5 to 5.5, and
the quotient (Q) is in the range from 0.8 to 1.2.
6. The Sinter Powder (SP) according to claim 1, wherein the median particle size (D50) of the Sinter Powder (SP) is in the range of 10 to 250 μm.
7. The Sinter Powder (SP) according to claim 1, wherein the Sinter Powder (SP) has:
d10 in the range of 10 to 60 μm,
d50 in the range of 25 to 90 μm, and
D90 in the range of 50 to 150 μm.
8. The Sinter Powder (SP) according to claim 1, wherein the Sinter Powder (SP) has a sintering window (W SP ) Wherein the sintering window (W SP ) Is the onset temperature of melting (T M2 Initiation ) With the onset temperature of crystallization (T C2 Initiation ) And wherein the sintering window (W SP ) In the range of 10 to 40K.
9. The Sinter Powder (SP) according to claim 1, wherein the Sinter Powder (SP) comprises:
10 to 90% by weight of component (A),
10 to 90% by weight of component (B),
0.1 to 1% by weight of component (C),
0.1 to 2.5% by weight of component (D), and
from 0 to 40% by weight of component (E),
in each case based on the total weight of the Sinter Powder (SP), the weight percentages of components (A), (B) and components (C), (D) and (E) generally adding up to 100% by weight.
10. A method of producing a shaped body comprising the steps of:
is) providing a layer of a Sintered Powder (SP) according to any of claims 1 to 9,
is) exposing the layer of Sintered Powder (SP) provided in step is) to form a shaped body.
11. A method of producing a shaped body comprising the steps of:
if) melting the Sinter Powder (SP) as claimed in any one of claims 1 to 9,
iif) depositing the melted Sintered Powder (SP) in the structural space to form a shaped body.
12. Use of a Sintering Powder (SP) according to any of claims 1 to 9 in a sintering process or in a fuse manufacturing process.
13. A method of preparing a Sintered Powder (SP) according to any one of claims 1 to 9 comprising the steps of:
a) Providing a first polyamide component (PA 1)
b) Providing a second polyamide component (PA 2)
c) The first polyamide component (PA 1) and the second polyamide component (PA 2) are mixed.
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| EP18196873.6 | 2018-09-26 | ||
| PCT/EP2019/075840 WO2020064825A1 (en) | 2018-09-26 | 2019-09-25 | Sinter powder (sp) comprising a first polyamide component (pa1) and a second polyamide component (pa2), where the melting point of the second polyamide component (pa2) is higher than the melting point of the first polyamide component (pa1) |
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| EP4279536A1 (en) | 2022-05-17 | 2023-11-22 | Ems-Chemie Ag | Materials for selective laser sintering and laser sintering using such materials |
| EP4316781A1 (en) | 2022-08-01 | 2024-02-07 | Arkema France | Method for manufacturing an article by material additive extrusion printing using a rheology modifier |
| WO2024108229A1 (en) * | 2022-11-19 | 2024-05-23 | MCANANY, Yuliya | Hybrid system for thermal additive manufacturing |
| EP4386036A1 (en) | 2022-12-15 | 2024-06-19 | Ems-Chemie Ag | Materials for selective laser sintering and laser sintering using such materials |
| EP4438654A1 (en) | 2023-03-29 | 2024-10-02 | Ems-Chemie Ag | Materials for powder bed fusion technologies and using such materials in a layer-by-layer process |
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- 2019-09-25 US US17/280,715 patent/US11939470B2/en active Active
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- 2019-09-25 JP JP2021517246A patent/JP7523433B2/en active Active
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| WO2017140764A1 (en) * | 2016-02-19 | 2017-08-24 | Basf Se | Kaolin for the mechanical reinforcement of polymeric laser sinter powder |
| WO2018019727A1 (en) * | 2016-07-29 | 2018-02-01 | Basf Se | Polyamide blends for laser sintered powder |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN112771118A (en) | 2021-05-07 |
| EP3856842B1 (en) | 2022-11-09 |
| WO2020064825A1 (en) | 2020-04-02 |
| US20220010133A1 (en) | 2022-01-13 |
| EP3856842A1 (en) | 2021-08-04 |
| JP2022516215A (en) | 2022-02-25 |
| US11939470B2 (en) | 2024-03-26 |
| JP7523433B2 (en) | 2024-07-26 |
| KR20210064326A (en) | 2021-06-02 |
| ES2934932T3 (en) | 2023-02-28 |
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